Fuel oil composition



Patented May 15, 1951 FUEL OIL COMPOSITION 'John B'. R. Caron, North Plainfield, N. J., Calmy Wies, New York, N. Y., and Everett B. Glendenning, Cranford, N. J assignors to Shell Development Company, San Francisco, Calif., a

corporation of Delaware No Drawing. Application July 3,1948, Serial No. 37,085

This invention pertains to improvement of hydrocarbon fuels, and more particularly to fuel oil compositions capable of preventing or inhibiting the sludging and/orclogging tendencies generally exhibited by hydrocarbon fuels, such as those utilized in burner systems, tanks, Diesel and combustion engines, and other industrial and domestic equipment. In addition, this invention relates to fuel oil compositions capable of removing preformed deleterious matter from filters, screens, and the like which deleterious matter is formed by deterioration and/or the presence of foreign bodies (e. g. water) in the fuel oils.

Hydrocarbons, such as distillate fuels, for example, those having a normal distillation range of from about 300 F. to about 700 F., and particularly those from about 340 F. to about 640 F., generally have a marked tendency to deteriorate under oxidizing conditions, and to form sludge; Also, the presence of impurities in such fuels, such as the presence of moisture, dispersed water, organic and/or inorganic foreign matter, and the like, causes the formation of insoluble products which tend to settle out and adhere to surfaces with which they come in contact, thereby in turn, causing clogging or plugging of filters, strainers, screens, conduit'lines, and the like, of the equipment in which they are used. This necessitates frequent'cleamng and even replac ment of parts, thereby markedly decreasing the performance eificiency of 'various equipment which utilizes such fuel oils.

The problem of screen clogging is common, particularly in domestic fuel oil systems employing distillate fuel Oils produced by distilling or cracking of petroleum, which fuels are characterized by their relativelylow-viscosity and other properties. Fuel oils of this type generally conform to the specifications setforth in Commercial Standards C. S. 12-40 for Nos. 1, 2, and 3, Fuel Oils. Petroleum. distillates within the ranges specified and which generally do not exceed 700 F., and preferablylare below 675 F., for use as Diesel fuels, are further examples of the, type of oils which under, conditions described herein have-a tendency to clog screens or filters, particularly when such fuels contain minor amounts of water dispersed therein.

Another place where screen clogging and plug-- ging of conduit. lines is encountered is in, fuel oil storage vtanks, which latter. may be connected to burner. systems. or .engines,.'etc. The stored fuel generallyrcomes in contact .withair, moisture, etc; i whichcause formation and precipita! 17 Claims; (01. 44-71) tion of sludge materials, the latter depositing on and clogging the screens or filters used for protecting the burners or engines using such fuel oils.

It is an object of this invention to inhibit sludging tendencies of hydrocarbon fuel oils. 7 It is another object to inhibit sludging and pre.-

cipitation of contaminants in hydrocarbon distillate fuel oils, particularly in cracked hydrocarbon fuels. vide distillate fuel oils, particularly fuel oils ob-. tained during cracking of hydrocarbons, which fuel oils have excellent performance characteristics with respect to freedom from screen clog ging, even after extensive storage under oxidiz ing, conditions and. in the presence of water.

dissolving in hydrocarbon fuel oils (which normally'have a tendency to cause clogging or plugging of screens or the like), a minor amount,

which amount, however, is sufficient to inhibit.

said tendencies of one or more surface-active glyoxalidines, and derivatives thereof. If desired, a minor amount of a detergent and/ or solutizer may also be added to the composition.

The hydrocarbon distillate fuel oils in which,

the active ingredient and/or ingredients of this invention are dispersed or dissolved may be treated or untreated cracked fuel oils, or mixtures of cracked fuels with straight run fuel oils, said fuel oils having components normally distilling from about 300 F. to about 700 F. Preferred fuels have a boiling range of from about 340 F. to about 700 F., and particularly from about 400 F. to about 675 F. Specifically, 'hydrocarbon distillates which are utilized as bases in compositions of this invention are cracked gasoils, fuel oils, furnace oils, burner oils, Diesel fuel oils, kerosene, etc., or mixtures of .said

cracked fuels with the corresponding or like straight run hydrocarbon fractions.

Fuel oils which have marked tendencies towards sludging and clogging of screens, filters,

etc., are primarily cracked or blends of cracked and straight run fuel oils which have the following properties: .1

It is still another object to pro- 3 Gravity, API 29-35 ASTM dist., F.:

IBP 400-500 EBP 600-700 Sulfur, percent w 0.5-1.05

Carbon residue (10, Btms.) per centw 0.1-1.4 Pour point, F -15 whereinonaR. represents hydrogen or R1 and R can'r'epresent, hydrogen or a lower alkyl group. and Rfrepreserits an alkylene group, a lower allsyl substituted alkylene group, or a radical of the structure -CHIR.;CHR1(NHCHR1CHR1)3/ where R1 also represents hydrogen or a lower allgyl. group. and J is an integer; and X represents a OHfSI-I, SeH, Tel-1,.NI-Izl group or an amino alkylene; substituent ir'nino. group. Specifically, the polyamines. which can be used are: ethylenediamine, diethylene triamine, triethylene tetraarnine; tetraethylene pentamine, tetramethyl methylenediamine, propylene diamine, dipropylene'f triamine, tripropylene tetramine, N-ndodecyl. diethylene triamine, N-octyle ethylene diami'rie, hydroxy. ethyl-ethylene diamine, hydrhxy. isopropyl propylene diamine, hydroxy ethyldiet hylene trlamine, hydroxy ethyl. triethylenev tetramine, N-beta-hydroxyepropyl propylene di amine'and. the like.

'Acids which, are reacted with the. above poly-. aminestolform the. glyoxalidines may include: capric, nonanoicj hendecanoic, lauric, n-tridecanoic, myristic, pentadecanoic, palrnitic, magaricf'stearic, arachidic, behenic, heneicosoic, chuytinic," lignoceric, pentacosic, cerotic, monta nic-,' palmito Ieic-, oleic, gadoleic, erucic, cetoleic, myristoleic', lanop'almic, hydroxy stearic, dihydrox-y stearic, ricinoleic acids, linoleic, elaidic, linole'nic; clupanodonic. acids. and the like. In. addition. fatty acids. obtained. from animal, vegee table. and fish. oils. can. be used and. the. fatty acids derived. from thefollowing fixed. fatty, oils. are, particularly preferred; cocoanut. oil, palm kernaloil. rape oil," linseedoil, soya, bean oil, sunflower. oil; perilla. oil, tung. oil, whale oil, cod and. cod. liver oil, marine-animal oil, variousfishoils.

suchas herring. oil, sardineoiland the like. In.- stead of using the free fatty acids, their salts, esters. or, amides can beused.

specific gly-oxalidines. which may be used in.

compositions of. this invention include:

l-amino ethyl ZeheptadecenyI' glyoxalidine l-amino ethylQ-heptadecyl glyoxalidine l-arriino-v ethyl 2 -undecyl glyoxalidine l-aminoisopropyl 2-h'eptadecenyl-5-methyl glyoxalidine.

l-a'm'ino isopropyl 2 -heptadecyl-5-methy1 gly The glyoxalidine having free amino group may be reacted with acid to form salts, while those glyoxalidines having free hydroxy or other groups can be esterified, with either inorganic or organic mono or polycarboxylic acids, or reacted to form salts of soaps of allgali, allgaline earth metals, ammonium, amine or quaternary ammonium compounds. If desired, and under certain conditions of use, it is preferred to add detergents to compositions of this. invention. The function of the detergent agents. compositions of this invention is to act as peptizers, aid; in inhibiting or preventing the. settling and adhering of impurities and sludge. to. surfaces and allow any impurities present or formed to pass through the screen or filter system.

Detergents which may be used are alkali, alkaline earth and heavy metals and organic nitrogen base salts of various organic acids. The Qi Q. Port on; Q .01 detergents may. bev naphh ni ce idi .n e acids arom i an h o r s acid aliphatic acid said; acids: containing, des r d substituent grou eamine h drox de. mem nt o and Sulfur qur nd he. i e Al p enates, c oletes. er a n th cerbam te xanthates. mar be. us

P rt er y pre err d. c ass: f e e nts. ar h sa ts. Q lkr z ubst t d ph nol sulfides; or. s; se eni e: n r tellm de equivalent. These. hen ic sa t may ba en esentedby theeneral: ormula whereinlyf isa metal; RrandR', represent at least one alkylradieal, attached to.the, aromatic ring.

the. total, number of carbon. atoms in all. of.

such rad-icalsv being, at, least, 5;, X is, O. and/ or S Q is S, Se or. Te and n. is aninteger of from. lto 4. To;form. the saltsofthesephenolic compounds.

" they may betreatedgwith, such. metal compounds wherein. the, symbols. are: the. sameas referred. toy in the.- previous... formulas; These-basic salts may be. formed by. reacting, theearomatic acidic com.- pounds. with; more. than the amount of' metal oxide. or.- hydroxide necessary to. form. the. normal.

salt.

Some specifimcompoundsas represented 'bythei above formulasare: barium tertiaryoctyl phenol: sulfide. and. disulfide, barium di-rtertiaryiamyl phenohsulfid; calcium. iso hexadecyl.phenorsulefide,v magnesium,tertiaryiamyliphenolj sulfide, co halt-tertiary amyllphenohsulfide, barium dodecyl.

salicylate. sulfide, sulfide oi thee barium salt of: the ethyl? esterof: pei-hydroxyi dithi'obenzoic acid;

calcium octyl phenol selenide, etc. The amount of detergent salt used may vary from between about 5 and 15% and preferably is kept below Another preferred class of detergents com- 5 prises the alkali (e. g. Na, K, Li) and/or alkaline Composition A earth metal (e. g. Ca, Sr, Ba, Mg) salts of pe- Per cent troleum sulfonic acids, preferably of high molecl-hydroxy ethyl-2-heptadecenyl glyoxalidine- 10 ular weight, derived from petroleum hydrocarbon Hydrocarbon fuel oil 90 crudes and fractions thereof which are of the 10 so-called mixed type, i. e. containing naphtheniccomposztwn B Per cent type hydrqcarbons' l-hydroxy ethyl-Z-heptadecyl glyoxalidine These oll-soluble petroleum sulfonates may Sodium petroleum sulfonate 10 be obtained by various processes, such as those Hydrocarbon fuel on 75 disclosed in the U. S. Patents, 2,388,677, 2,395,713, 15 2,413 713 2 413 311 2 414 773 231 397 and if Compositions of this invention are generally desired, purified by such means as those disclosed mixed in amounts of one p less With from in U. S. Patents, 2,236,933, 2,334,532, 2,357,3 about 250 to about 1000 gallons of fuel oil. Thus, 2 3 3 452 and 2 40 753 for example, on a percentage basis of fuel used, The metal Salts of 1 pe ifi type of Petro- 20 one pint of any one of the above compositions, for 1 lfoni acid under discussion, or the other example per 250 gallons of fuel would correspond types of detergents may be added to the to approximately the following concentration of centrate or base in amounts of fr about 5 theactive ingredients: Organic nitrogenous comto about 15%, and preferably in amounts below Pounds as described 0-0O25% detergent 0 to 0 about 0.0025%; drying agent, 0 to about 0.265%.

In Systems wherein substantial amounts of To inhibit any corrosive tendencies of fuelcommoisture are present a drying agent may be positions of this invention, a minute amount of added which is compatible with the active caustic or aromatic nitrogen compounds such as gredients of this invention. By tying up most of amlme may be added- These compounds 3F as the free moisture in this manner the amount alkaline reserves and render the fuel composltions which would normally combine with syudgek substantially non-corrosive to copper; brass, and forming materials is diminished, thus alleviating other metalsg a most aggravating clogging problem The following illustrates the effectiveness of Drying agents which are particularly Suited are compositions of this 1nvent1on as sludge inhibithe glycol-ether type such as diethylene-glycol tors and antlcloggmg agentsmono-methyl, ethyl N- and isopropyl ether, di- Examp I M ethylene glycol mono'butyl ether, methylene To a number of sample bottles each containyc01 mo y ether, 8170- also dipropylene ing approximately 50 cc. of fuel oil normally sus glycol mono'ethyl ether, dipropylene glycol ceptible to cause clogging a minute amount of mono-isopropyl ether. dipropylene glycol monoabout 0.15 cc. of water was added and also to isoamyl ether. diisoblltylene yc mOIIO-iSO- each sample bottle about 0.05% of a specific base P DY ether, y -p pylene glycol O composition as noted in the table below was also ethyl ether, y sobu ylene glycol m0 added. The bottles were shaken thoroughly and p opy et e e170- IIlStead 0f the y -fi e I then permitted to stand for about one hour. Sus- Various alcohols may be us Such a 61 8 having pension properties of water and inert particles 6 or more carbon atoms in the m l ule su h as were observed and noted after one hour. After ylene gly y e e ycol, cetylene g yc one hour of standing the bottles were shaken etc. diglycols such as dipropylene glycol, dibuty1 again and the contents poured into a very fine ene glycol, diamylene glycol, ether alcohols and strainer container. Wetting and drainage propparticularly the glycol mono-alkyl ethers, e. g. erties on the bottle were observed just before and the cellosolves such as ethylene glycol monoafter removal of contents. The time of efflur ethyl ether, ethylene glycol mono-propyl ether, of the composition was noted for each composiethylene glycol mono-tert-butyl ether, ethylene tion and the condition of the strainer observed. glycol mono-butyl ether, propylene glycol mono- Emlmple H ethyl ether propylene glycol monods-oamyl ether Another test, the results of which are also tabetc. Also glycol mono-tert-butyl ether, ethylene ulated below, in order to determine the eifectweglycol mono-hexyl-butyl ether, propylene glycol f f f mono-isoamyl ether, etc. Also glycerine and the ness 9 compos 0 1S H.1Ven Ion or an d sludgmg and clogging properties was conducted like may be 1 f b in the following manner: About 0.05% of base The fiq a.gener.a1 o ase compositions of this invention was added to fuel composltwn of thls mventlon' oils containing entrained moisture. The sam- Per cent ples were allowed to age for two days. These Surfac ct v agent y d cs a samples were then shaken and evaluated for their derivatives thereof ;4-20 anti-clogging properties, as related in the pre- 6 Drying agent e. g. glycol-ether 0-50 Hydrocarbon fuel oil Balance Specific base (concentrate) compositions may be illustrated by the following examples:

Detergent e. g. phenate, sulfonate, etc -i0-=10 ceding para raph- 0.05% or less base composition as noted in fuel oil containing en- Properties evaluated immediately after adding concentrate to fuel oil Same properties after aging of doped fuel oil Example I Example II trained moisture asserts "irocompositions .ofzthis -inventionz=may be added minor :amounts .of .a .foaming inhibitor :such as silicon liquids, .e. g. .dimethyl silicone, fiuoro .organic compounds, chloro parafifins, salts .of alkyl alkylene phosphates and the like. Compositions of this invention may be used -to remove deposits, formedon metal surfaces such as in tubes, evaporators, heat exchangers, distillation an'dacracking equipment-and the like. They are non-corrosive and do not interfere with the functioning of the liquid .in which dispersed.

It is to .be understood that while .the features of the invention have been-described and illustrated in connection with certain specific examples, this invention, however, is not to'be limited thereto or otherwise restricted, except by the prior art and the scope of the appended-claims.

We claim as our invention:

"1. Anon-clogging fuel oil containing entrained moisture-and normally susceptible 'to cause clogging containing in combination therewith from about 0.0025% to about 0.005% of l-aminoethyl- 2-heptadecenyl glyoxalidine.

'2. Anon-clogging fuel oil containingentrained moisture and normally susceptibleto cause clogging containing in combination therewith from about 0.0025% toabout 0.005% of l-aminoethyl- 2-heptadecenyl glyoxalidine and about 0.0025% of alkali metal petroleum sulfonate.

3. Anon-cloggingfuel oil containing 'entrained moisture and normally susceptible to cause clo ging containing in combination therewith from about0.0025% to about 0.005% of l-aminoethyl- Z-heptadecenyl glyoxalidine, and about-0.0025% of metal salt of alkyl phenol disulfide.

4. An anti-cloggingconcentrate adapted to be added to -a hydrocarbon fuel oil containing cracked components, said concentrateconsisting essentiallyof a major amount .ofa liquid hydrocarbon distillate iraction and to of l-amino-ethyl-Z-heptadecenyl glyoxalidine.

5. An anti-clogging concentrate adapted to be added to a hydrocarbon fuel 011 containing cracked components, said concentrate consisting-essentially of amajor amountof-a-liquid hydrocarbon distillate fraction and 10% to 20% .of l-amino-ethyl-Zeheptadecenyl glyoxalidine'and va metal salt of alkyl phenol disulfide.

6. An anti-clogging concentrate'adapted to be added to a hydrocarbon fuel 'oil containing cracked components, said concentrate comprising as an essential ingredient a major amount of a liquid hydrocarbon distillate fraction and 10- 20% by weight of a glyoXalidine bearing at least one higher aliphatic hydrocarbon radical and in additionthereto a radical of the group consisting of lower amino alkyl and lower hydroxy alkyl substituents and salts thereof.

'7. A non-clogging fuel oil containing'entrained moisture and normally susceptible to cause clogging containing in combination therewith from about 0.0025% to about 0.005% of a glyoxalidine bearing at least one higher aliphatic hydrocarbonradical and in addition thereto a radical .of the group consisting of lower amino alkyl and lower hydroxy alkyl substituents and 'salts thereof.

8 i8. .Aiconcentrate according ztoicla'im 5'6 containing )in addition up 'to 10% :by :weight :of ;a metal sal-t of an alkyl phenoldisulfide.

9. A concentrate according to claim 6 containing addition thereto up to :50 by weight :of a glycol "ether .as a drying agent.

:10. A hon-clogging .fuel oil containing 'en trained moisture and normally susceptible to cause clogging containing in combination "therewith about 0.002% to 0.005% of :l-aminoethyl- 2-heptadecenylglyoxalidine and-about 0;0025% 'of sodium petroleum sulfonate.

11.A non-clogging fuel oil :containin'g entrained moisture and normally susceptible to cause clogging containing in combination therewith about 0.002% to 0.005% of -l-amin'oe'thyl- 2--heptadecenyl glyoxalidine and about 0.0025% of barium alkyl phenol disulfide. V

12. An anti-clogging concentrate adapted to be added to a hydrocarbon fuel oil containing cracked components, said concentrate consisting essentially of a ma'jor-amount of a liquid hydrocarbon distillate fraction and 10% to 20% of 1 aminoethyl-2-heptadecenyliglyoxalidine and an alkali metal petroleum sulfonate.

13. An-anti-clogg'ing concentrate adapted to be added" to a hydrocarbon fuel oil containing cracked components, said concentrate'consisting essentially of a major amount of a 'liquid'hydrocarbon distillate fraction and 10% to 20% of 1 aminoethyl 2 heptadecenyl glyoxalidine and barium salt of alkyl-phenol disulfide.

14. An anti-clogging concentrate adapted be .added to a hydrocarbon fuel oil contairiing cracked components, said concentrate consisting essentially of a major-amount of 1 a liquid hydro-- carbon distillate fraction and 10% to 20% of 1--aminoethyl-2-heptadecenyl glyoxalidine .and sodium petroleum isulfonate.

15. A concentrate according to claim 6 con-' taining in'addition :up .to 10% by .weight of :an

alkali metal petroleum sulfonate.

.16. A non-clogging .fuel oil containing entrained .moisture and :normally susceptible it!) cause clogging containing iin combination there with from about 0.0025% to about 0.005% ofl-hydroxyethyl-Z-heptadecenyl :glyoxalidine.

.17. A non-clogging fuel -:oil containing entrained :moisture and normally susceptible itO cause clogging containing in combination there- REFERENCES CITED The following :references are of record in ithe file of this patent:

UNITED STATES PATENTS Number Name Date 2,249,626 Cooketal July'15, 1941 2,369,490 -Proell -Feb. 13,1945 

1. A NON-CLOGGING FUEL OIL CONTAINING ENTRAINED MOSITURE AND NORMALLY SUSCEPTIBLE TO CAUSE CLOGGING CONTAINING IN COMBINATION THEREWITH FROM ABOUT 0.0025% TO ABOUT 0.005% OF 1-AMINOETHYL2-HEPTADECENYL GLYOXALIDINE. 